EP0435019A1 - Article, en particulier came, en alliage de poudre frittée, et son procédé de préparation - Google Patents

Article, en particulier came, en alliage de poudre frittée, et son procédé de préparation Download PDF

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Publication number: EP0435019A1
Authority: EP; European Patent Office
Prior art keywords: copper; wear; iron; powder; molybdenum
Prior art date: 1989-12-20
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Granted

Application number

EP90123087A

Other languages

German (de)

English (en)

Other versions

EP0435019B1 (fr

Inventor

Karl Leithner

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Supervis

Original Assignee

Supervis

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1989-12-20

Filing date

1990-12-03

Publication date

1991-07-03

1990-12-03 Application filed by Supervis filed Critical Supervis

1991-07-03 Publication of EP0435019A1 publication Critical patent/EP0435019A1/fr

1995-05-17 Application granted granted Critical

1995-05-17 Publication of EP0435019B1 publication Critical patent/EP0435019B1/fr

2010-12-03 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

239000000843 powder Substances 0.000 title claims description 18
238000004519 manufacturing process Methods 0.000 title claims description 6
229910001092 metal group alloy Inorganic materials 0.000 title 1
239000010949 copper Substances 0.000 claims abstract description 76
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 74
229910052802 copper Inorganic materials 0.000 claims abstract description 72
XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 39
229910052750 molybdenum Inorganic materials 0.000 claims abstract description 26
ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 25
229910045601 alloy Inorganic materials 0.000 claims abstract description 23
239000000956 alloy Substances 0.000 claims abstract description 23
239000011733 molybdenum Substances 0.000 claims abstract description 22
229910052742 iron Inorganic materials 0.000 claims abstract description 17
PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 15
239000011159 matrix material Substances 0.000 claims abstract description 13
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
229910052799 carbon Inorganic materials 0.000 claims abstract description 9
229910052759 nickel Inorganic materials 0.000 claims abstract description 8
VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
229910052804 chromium Inorganic materials 0.000 claims abstract description 6
239000011651 chromium Substances 0.000 claims abstract description 6
238000002485 combustion reaction Methods 0.000 claims abstract description 6
WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
229910052710 silicon Inorganic materials 0.000 claims abstract description 5
239000010703 silicon Substances 0.000 claims abstract description 5
238000005245 sintering Methods 0.000 claims description 14
238000000034 method Methods 0.000 claims description 13
239000011148 porous material Substances 0.000 claims description 12
238000000465 moulding Methods 0.000 claims description 3
238000002791 soaking Methods 0.000 claims description 3
DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 claims 3
238000005255 carburizing Methods 0.000 claims 1
229910002804 graphite Inorganic materials 0.000 claims 1
239000010439 graphite Substances 0.000 claims 1
238000002156 mixing Methods 0.000 claims 1
238000004663 powder metallurgy Methods 0.000 abstract description 3
239000000314 lubricant Substances 0.000 description 9
229910000734 martensite Inorganic materials 0.000 description 9
239000000463 material Substances 0.000 description 8
239000003921 oil Substances 0.000 description 8
239000007787 solid Substances 0.000 description 8
238000005498 polishing Methods 0.000 description 7
238000012360 testing method Methods 0.000 description 7
229910000831 Steel Inorganic materials 0.000 description 6
239000010959 steel Substances 0.000 description 6
230000007423 decrease Effects 0.000 description 5
238000005461 lubrication Methods 0.000 description 5
230000008569 process Effects 0.000 description 5
XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
239000000654 additive Substances 0.000 description 4
239000000853 adhesive Substances 0.000 description 4
230000001070 adhesive effect Effects 0.000 description 4
238000009792 diffusion process Methods 0.000 description 4
238000009826 distribution Methods 0.000 description 4
150000001247 metal acetylides Chemical class 0.000 description 4
229910017116 Fe—Mo Inorganic materials 0.000 description 3
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
238000004090 dissolution Methods 0.000 description 3
230000000694 effects Effects 0.000 description 3
238000001000 micrograph Methods 0.000 description 3
229910052760 oxygen Inorganic materials 0.000 description 3
239000001301 oxygen Substances 0.000 description 3
239000002245 particle Substances 0.000 description 3
238000010791 quenching Methods 0.000 description 3
230000000171 quenching effect Effects 0.000 description 3
238000005496 tempering Methods 0.000 description 3
PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
239000003082 abrasive agent Substances 0.000 description 2
239000003570 air Substances 0.000 description 2
238000005275 alloying Methods 0.000 description 2
229910052786 argon Inorganic materials 0.000 description 2
230000008901 benefit Effects 0.000 description 2
238000005516 engineering process Methods 0.000 description 2
238000005470 impregnation Methods 0.000 description 2
230000001788 irregular Effects 0.000 description 2
229910052748 manganese Inorganic materials 0.000 description 2
239000011572 manganese Substances 0.000 description 2
238000005259 measurement Methods 0.000 description 2
239000000203 mixture Substances 0.000 description 2
238000003825 pressing Methods 0.000 description 2
230000008961 swelling Effects 0.000 description 2
229910001018 Cast iron Inorganic materials 0.000 description 1
229910000881 Cu alloy Inorganic materials 0.000 description 1
101100229963 Drosophila melanogaster grau gene Proteins 0.000 description 1
229910000640 Fe alloy Inorganic materials 0.000 description 1
229910001182 Mo alloy Inorganic materials 0.000 description 1
OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
229910018540 Si C Inorganic materials 0.000 description 1
241000607479 Yersinia pestis Species 0.000 description 1
238000005299 abrasion Methods 0.000 description 1
238000007792 addition Methods 0.000 description 1
230000002730 additional effect Effects 0.000 description 1
230000000996 additive effect Effects 0.000 description 1
238000004458 analytical method Methods 0.000 description 1
238000000137 annealing Methods 0.000 description 1
238000013459 approach Methods 0.000 description 1
239000011230 binding agent Substances 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
230000008859 change Effects 0.000 description 1
238000011109 contamination Methods 0.000 description 1
IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
238000001739 density measurement Methods 0.000 description 1
238000011161 development Methods 0.000 description 1
230000018109 developmental process Effects 0.000 description 1
238000002474 experimental method Methods 0.000 description 1
238000013213 extrapolation Methods 0.000 description 1
238000005242 forging Methods 0.000 description 1
238000000227 grinding Methods 0.000 description 1
238000000265 homogenisation Methods 0.000 description 1
230000007246 mechanism Effects 0.000 description 1
229910052751 metal Inorganic materials 0.000 description 1
239000002184 metal Substances 0.000 description 1
150000002739 metals Chemical class 0.000 description 1
230000035515 penetration Effects 0.000 description 1
238000010587 phase diagram Methods 0.000 description 1
229910052698 phosphorus Inorganic materials 0.000 description 1
239000011574 phosphorus Substances 0.000 description 1
238000004445 quantitative analysis Methods 0.000 description 1
239000004576 sand Substances 0.000 description 1
238000012031 short term test Methods 0.000 description 1
229910010271 silicon carbide Inorganic materials 0.000 description 1
238000010245 stereological analysis Methods 0.000 description 1
238000005482 strain hardening Methods 0.000 description 1
230000035882 stress Effects 0.000 description 1
230000008646 thermal stress Effects 0.000 description 1
230000007704 transition Effects 0.000 description 1
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
238000003466 welding Methods 0.000 description 1

Images

Classifications

- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/08—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of toothed articles, e.g. gear wheels; of cam discs
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements

Definitions

the invention relates to a molded part, in particular a cam made of a sintered, powder-metallurgically produced alloy for a modular camshaft for internal combustion engines, and to a method for its production.
camshafts of camshafts for internal combustion engines are exposed to very heavy wear.
the wear In order to fulfill their task of engine control, the wear must not exceed a few ⁇ m during their entire service life. Load cycles with insufficient lubrication must also be endured.
the usual method in literature and technology is the use of high-carbide alloys, which are either produced by powder metallurgy from appropriate materials or by rapid quenching of cast iron. This means that both abrasive and adhesive wear can be kept within limits.
the cams are also exposed to thermal stress. For this reason, the cams have to be so hard that they can maintain them even after a long start. This can be achieved by hardening and then tempering at a temperature above the operating temperature.
the cams should also exhibit excellent operating behavior under operating conditions in which there is insufficient lubrication and which promote adhesive wear.
the polishing wear is an appearance of the abrasive wear, in which there is very little abrasion with a small corrugation width due to the appropriately fine abrasive materials.
the cam which has been worn out in this way appears to be polished to a polished finish, the roughness of the worn areas usually being much smaller than that of the undamaged (ground) areas.
the polishing wear can be caused as three-body wear by quartz dust in the oil. Sand is one of the most common abrasives that occur in engineering. Since the polishing wear also occurs under test conditions in which contamination of the oil can be ruled out, there must also be another mechanism. Obviously, the polishing wear can also be promoted by a hard, rough counterpart that contains no carbides.
Eating is a result of adhesive wear, i.e. the mutual welding of the surfaces. It is favored by the use of martensitic base and counter bodies (8) and by the use of unalloyed oil. Experiments with increased spring force of the valve spring also favor seizure. While in forty-three pairs twenty-six failed to eat when unalloyed oil was used, not a single pair failed to eat when using alloyed oil (8). However, the failure due to pitting in alloyed oil increased from seventeen pairs to thirty-five pairs (8).
Molybdenum is found in many P / M steels. The reason for the frequent use of 0.5% molybdenum is certainly of a purely practical nature. Commercial base iron powder contains 0.5% molybdenum. A conscious admixture only happens in the rarest of cases. Fe-P-Cu-Mo alloys with Cu contents up to 4% and Mo contents between 2% and 4% have also been investigated (17). All alloying elements were mixed in elementally. The samples with 2% Mo and 4% Cu have an irregular two-phase structure after sintering at 1200 C for one hour. This inhomogeneity becomes even clearer when the Mo content is increased to 4%. Carbon slows down the diffusion of Cu into Fe, but it does not prevent complete dissolution.
the invention is based on this prior art, which aims to improve the emergency running properties of a cam, which is achieved according to the invention in that the alloy has a hardened matrix with embedded copper and from 0.5-16% by weight molybdenum , 1 - 20% by weight of copper, 0.1 - 1.5% by weight of carbon and optionally from admixtures of chromium, manganese, silicon and nickel of a total of max. 5 wt .-% and consists of the rest of iron.
the additives are used to adapt the alloy to the application in terms of secondary hardness, strain hardening and hardenability.
a sinter powder made of 0.5-16% by weight of molybdenum, 1-20% by weight of copper, 0.1-1.5% by weight of carbon and optionally from admixtures of Chromium, manganese, silicon and nickel of a total of max. 5 wt .-% and from the rest of iron to a cam molding with a green density above 7 g / cm 3 is pressed and sintered at temperatures below 1150 ° C for a sintering time of 10 to 60 minutes and then tempered.
FIG. 1 is an enlargement on a scale of 200: 1;
Fig. 2 is an enlargement of the same micrograph on a scale of 500: 1.
the martensite has a very even appearance. No inhomogeneities can be seen. This corresponds to the expectations, since a pre-alloyed, i.e. already homogeneous powder was used.
the copper is present in irregular spots evenly distributed over the structure.
the size of the copper grains is 10 to 30 ⁇ m.
the pores are well rounded. They are distributed bimodally. One size range is around the value normally observed for steels of 5 ⁇ m, the second is around 50 ⁇ m.
the large pores are secondary pores that result from the dissolution of copper.
microhardness was less than 50 HV0.01. Since the phase was very finely divided, the diagonals of the impressions were almost as large as the areas themselves, so that an exact specification of the microhardness is not possible.
the hardness of pure copper is 34 HV (38).
the light areas are copper and not carbides or an alloy of copper and iron or an intermetallic phase of iron and molybdenum. In any case, there should be no doubt about the identity of the pores and the martensite.
the martensitic areas in the core had a hardness of just under 400 HV0.01.
the macro hardness HV10 was determined to be 372. The hardness values were measured in the core.
the volume fraction of the undissolved copper was determined.
the copper content was 7.8% by volume.
the chemically analyzed copper content was determined to be 7.4% by weight.
the density of copper is somewhat greater than that of iron, so that a larger proportion would be derived from stereological analysis.
the results from the two analyzes can be regarded as the same. This means that the copper is completely undissolved, the matrix is probably completely free of Cu.
the volume fraction of the pores was also determined stereologically and using gravimetric density measurements. The corresponding value was 6.5%.
the alloy Fe / 1.5Mo / 10Cu / 0.8C consists, in addition to a small proportion of pores, of elemental copper and martensite, in which only a negligible proportion of copper is dissolved. While the pores on the surface improve the lubrication somewhat, the copper content serves as a solid lubricant to improve the emergency running properties.
the martensite causes the resistance to abrasive wear.
molybdenum Only molybdenum can be held responsible for this.
the insolubility of copper in molybdenum (34) suggests that molybdenum greatly reduces the solubility of copper in iron. If one looks at a phase diagram of Fe-Mo, it is noticeable that the transition from gamma to a-iron takes place at 2.6% by weight (1.5 at.%) Mo in the range around 1100 ° C. Molybdenum is therefore a very strong ⁇ -opener, i.e. the steel is preferably in the krz structure.
the solubility of copper in iron is much lower in the a phase than in the automotive gamma phase: While up to 7.5% by weight dissolves in gamma iron, the maximum solubility in the a phase is only 1.4% by weight (36). The fact that the a-phase is largely stabilized by the molybdenum (1.5% by weight) largely prevents the copper from diffusing in. However, copper is obviously not completely insoluble in Fe-Mo. In the Fe-1% Mo system, the diffusion coefficient of copper was measured (37), which suggests that finite solubility for copper exists at least at these small molybdenum concentrations.
the upper limit is rather set by economic considerations.
the Mo content will therefore be limited to around 16%.
the a region is left at the sintering temperature (1120 C), which can lead to a change in the behavior of the alloy. This limit could therefore be called the upper limit.
the copper content must be selected so that it guarantees the required emergency running properties.
the lower limit can be set at around 1%, since the effect of copper as a solid lubricant will hardly suffice.
a value must be chosen as the upper limit, in which a sufficient part of the structure is still present in the form of the hard martensitic matrix, in order to guarantee that the supporting surface remains sufficiently large. In terms of magnitude, an upper limit of 20% can be assumed.
the alloy according to the invention can only be produced by powder metallurgy.
the special structure which consists of a martensitic matrix and elementary copper, is created directly by the sintering process.
the extremely low solubility of copper in Fe-Mo is exploited, which means that the copper content is practically completely available as a solid lubricant and does not lead to swelling as is the case with Cu-alloyed materials. It can be assumed that a comparable structure is obtained when using a mixed or diffusion alloy powder.
Molybdenum very effectively prevents the copper from dissolving in the matrix, so that the copper can be available as a solid lubricant.
a solid lubricant By using a solid lubricant, a major problem of wear in the cam-counter body system, the adhesion, is successfully solved.
the molybdenum prevents the swelling otherwise observed in copper-alloyed materials. This increases the working accuracy and improves the mechanical properties.
a ge mixed alloy Fe-C-Mo powder is first solidified by sintering and homogenized. By choosing a very low green density, open pores remain in the structure, which are closed by impregnation with copper. A comparable structure can also be created in this way. A pre-alloyed powder can also be assumed in this process variant.

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Chemical & Material Sciences (AREA)
Engineering & Computer Science (AREA)
Mechanical Engineering (AREA)
Materials Engineering (AREA)
Metallurgy (AREA)
Organic Chemistry (AREA)
Manufacturing & Machinery (AREA)
Powder Metallurgy (AREA)
Valve-Gear Or Valve Arrangements (AREA)
Gears, Cams (AREA)

EP90123087A 1989-12-20 1990-12-03 Article, en particulier came, en alliage de poudre frittée, et son procédé de préparation Expired - Lifetime EP0435019B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DE3942091A DE3942091C1 (fr)	1989-12-20	1989-12-20
DE3942091		1989-12-20

Publications (2)

Publication Number	Publication Date
EP0435019A1 true EP0435019A1 (fr)	1991-07-03
EP0435019B1 EP0435019B1 (fr)	1995-05-17

Family

ID=6395899

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP90123087A Expired - Lifetime EP0435019B1 (fr)	1989-12-20	1990-12-03	Article, en particulier came, en alliage de poudre frittée, et son procédé de préparation

Country Status (7)

Country	Link
US (1)	US5082433A (fr)
EP (1)	EP0435019B1 (fr)
JP (1)	JPH03291361A (fr)
KR (1)	KR0183390B1 (fr)
CA (1)	CA2032300C (fr)
DE (2)	DE3942091C1 (fr)
ES (1)	ES2075122T3 (fr)

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GB9021767D0 (en) *	1990-10-06	1990-11-21	Brico Eng	Sintered materials
JP2713658B2 (ja) *	1990-10-18	1998-02-16	日立粉末冶金株式会社	焼結耐摩摺動部材
JP3520093B2 (ja) *	1991-02-27	2004-04-19	本田技研工業株式会社	二次硬化型高温耐摩耗性焼結合金
US5256184A (en) *	1991-04-15	1993-10-26	Trw Inc.	Machinable and wear resistant valve seat insert alloy
ATE195276T1 (de) *	1992-12-21	2000-08-15	Stackpole Ltd	Verfahren zur herstellung von lagern
US5293847A (en) *	1993-02-16	1994-03-15	Hoffman Ronald J	Powdered metal camshaft assembly
US5834640A (en) *	1994-01-14	1998-11-10	Stackpole Limited	Powder metal alloy process
CA2182389C (fr) *	1994-02-07	2001-01-30	Rohith Shivanath	Alliage fritte haute densite
AT405916B (de) *	1995-02-16	1999-12-27	Miba Sintermetall Ag	Verfahren zum herstellen eines nockens für eine gefügte nockenwelle
US6210503B1 (en)	1997-11-13	2001-04-03	Cummins Engine Company, Inc.	Roller pin materials for enhanced cam durability
JPH11280419A (ja) *	1998-03-31	1999-10-12	Sumitomo Electric Ind Ltd	シムとカムの組合せ体
DE19858483A1 (de) *	1998-12-18	2000-08-31	Mannesmann Rexroth Ag	Hydraulische Verdrängermaschine, insbesondere Verdrängerpumpe
JP2000192110A (ja) *	1998-12-22	2000-07-11	Honda Motor Co Ltd	カムシャフトの製造方法
JP2001090808A (ja) *	1999-09-21	2001-04-03	Toyota Motor Corp	３次元カム及びその製造方法
JP3835103B2 (ja) *	2000-01-28	2006-10-18	スズキ株式会社	焼結合金及びその硬化処理方法
SE0203135D0 (sv) *	2002-10-23	2002-10-23	Hoeganaes Ab	Dimensional control
JP4115826B2 (ja) *	2002-12-25	2008-07-09	富士重工業株式会社	アルミニウム合金鋳包み性に優れた鉄系焼結体およびその製造方法
JP4799006B2 (ja) *	2004-03-01	2011-10-19	株式会社小松製作所	Ｆｅ系シール摺動部材およびその製造方法
JP4799004B2 (ja) *	2004-03-08	2011-10-19	株式会社小松製作所	Ｆｅ系シール摺動部材及びその製造方法
JP4820562B2 (ja) *	2004-04-05	2011-11-24	株式会社小松製作所	Ｆｅ系耐摩耗摺動材料および摺動部材
DE102004028221A1 (de) *	2004-06-09	2005-12-29	Ina-Schaeffler Kg	Hochbeanspruchtes Motorenbauteil
TWI325896B (en)	2005-02-04	2010-06-11	Hoganas Ab Publ	Iron-based powder combination
KR100966266B1 (ko) *	2009-11-16	2010-06-28	(주)씬터온	소결경화된 분말금속부품의 제조방법
DE102011109473A1 (de)	2011-08-04	2012-03-15	Daimler Ag	Sinterbauteil und Nockenwelle
JP5936954B2 (ja) *	2012-08-23	2016-06-22	Ntn株式会社	機械部品の製造方法
CN115094390A (zh) *	2014-09-30	2022-09-23	捷客斯金属株式会社	溅射靶用母合金和溅射靶的制造方法
CN105149595A (zh) *	2015-08-28	2015-12-16	苏州莱特复合材料有限公司	一种粉末冶金轴套及其制备方法
JP7354996B2 (ja) *	2020-11-30	2023-10-03	Ｊｆｅスチール株式会社	鉄基合金焼結体及びその製造方法
CN118007029A (zh) *	2024-04-09	2024-05-10	广东美的制冷设备有限公司	用于3d打印注塑模具的铁铜钼合金模具钢及其制备方法和应用

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1989
- 1989-12-20 DE DE3942091A patent/DE3942091C1/de not_active Expired - Fee Related
1990
- 1990-12-03 EP EP90123087A patent/EP0435019B1/fr not_active Expired - Lifetime
- 1990-12-03 DE DE59009097T patent/DE59009097D1/de not_active Expired - Lifetime
- 1990-12-03 ES ES90123087T patent/ES2075122T3/es not_active Expired - Lifetime
- 1990-12-13 CA CA002032300A patent/CA2032300C/fr not_active Expired - Lifetime
- 1990-12-17 US US07/629,230 patent/US5082433A/en not_active Expired - Lifetime
- 1990-12-19 JP JP2403737A patent/JPH03291361A/ja active Pending
- 1990-12-20 KR KR1019900021200A patent/KR0183390B1/ko not_active Expired - Lifetime

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EP0435019B1 (fr)	1995-05-17
US5082433A (en)	1992-01-21
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ES2075122T3 (es)	1995-10-01
KR910011370A (ko)	1991-08-07
CA2032300A1 (fr)	1991-06-21
DE59009097D1 (de)	1995-06-22
JPH03291361A (ja)	1991-12-20
CA2032300C (fr)	2001-07-24

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